Stabilizer for halogen-containing polymers



Patented Jan. 19, 1954 2,666,752 STABILIZER FOgQlEALOGEN-CONTAINING YMERS Oliver J. Grummitt and Robert E. Blank, Cleveland, Ohio, and Herbert F. Schwarz, Flossmoor,

Ill., assignors to The Sherwin-Williams Company, Cleveland, Ohio, a corporation of Ohio No Drawing. Application January 1'7, 1950,

Serial No. 139,127

9 Claims. (Cl. 260-23) This invention relates as indicated to synthetic resins, and is primarily concerned with compositions of the halogen-containing polymer type which are beneficially stabilized in that they are remarkably resistant to decomposition ordinarily induced by heat and light.

Polymeric compositions containing halogen atoms such as fluorine, chlorine, and bromine deteriorate on exposure to heat and/or light. Such exposure, especially to heat, frequently occurs during fabrication of the material, and light exposure may occur throughout the life of the material. These conditions result in discoloration, embrittlement, and loss of strength in cast or extruded films, coatings, etc. invention concerns agents which will inhibit or efiectively retard this deterioration'in halogencontaining polymers in extruded sheets, molded objects, unsupported films, coated fabrics and coating compositions. A further object is to provide agents which do not alter substantially the transparency of clear polymers or the color of pigmented polymers. It is also an object of this invention to provide an agent which is compatible with halogen-containing polymers in composition with other ingredients such as plasticizers, alkyd resins, phthalates, phosphates, pigments, and the like. Other objects of this invention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, said invention, then, consists of the means hereinafter fully described and particularly pointed out in the appended claims, the following description setting forth in detail certain embodiments of the invention, such disclosed Q means constituting, however, but a few of the various forms in which the principle of our invention may be employed.

Broadly stated, our invention is in the provision of a composition comprising a halogen containing polymer and an aliphatic acid ester of a polyhydric alcohol in which ester from about 25% to below 75% of the available free hydroxyl groups have been acylated with an aliphatic acyl compound having the general formula where R is an aliphatic acyl radical of 1 to 6 carbon atoms, and X;ls selected from -011, -SH, O-R,---SR, and, halogen. More mm- This ticularly, our invention is in the provision of a composition having as a major constituent thereof a polyvinyl halide, which composition has been stabilized with from .1 to 10 parts per 100 parts of polymer of an agent consisting of the partial esters of polyhydric alcohols and the acids of animal and vegetable oils in which ester from 25% to below 75% of the available hydroxyl groups have been acylated by interaction with another fatty acid or fatty acid anhydride containing from 1 to 6 carbon atoms in the acyl group.

We have discovered that highly effective heat and light stabilizing agents consist of partial esters of polyhydric alcohols with fatty acids in which only a portion of the free hydroxyl groups have been esterified by a low molecular weight fatty acid or low molecular weight fatty acid anhydride. The higher molecular weight fatty acids from which the partial esters are formed may include any of those found in the naturally occurring animal and vegetable oils such as lauric, palmitic, stearic, oleic, linoleic, linolenic, ricinole ic, dihydroxystearic, etc. The polyhydric alcohol may be a glycol such as ethylene glycol, propylene glycol, or glycerol, trimethylolethane, pentaerythritol, mannitol, sorbitol, and the like. The low molecular weight fatty acids useful in accordance with this invention generally contain in the acyl group or each acyl group, as the case may be, from 1 to 6 carbon atoms. In general, any aliphatic compound capable upon reaction of yielding to the partial ester above described an acyl radical of from 1 to 6 carbon atoms may be used and such aliphaticcompound may be in the form of a carboxylic acid, the anhydride, or

' the acid halide, e. g. chloride or bromide. We

may also use the thio analogues of the acid and anhydride, e. g. the thiol carboxylic acids and the thiol anhydrides yielding acyl groups of from 1 to 6 carbon atoms. Specific examples of such materials include formic acid, acetic acid, acetic anhydride, acetyl chloride, propionic acid, thiol propionic acid, propionyl chloride, butyric acid, iso-butyric acid, thiol butyric acids, pentanoic acids, thiol pentanoic acids, hexanoic acids, etc. The presence of halogen atoms in the molecules of these aliphatic acyl providing compounds in w an inactive position, such as the omega position on the 4, .5, and 6 carbon atom acyl radical pro- U viding compounds, as well as the presence of oxygen in the form of keto or ether groups in the aliphatic residue of the acid may be tolerated, although we prefer the alkyl acids and anhydrides having from 1 to 5 carbon atoms in each acyl group, and particularly acetic acid and acetic anhydride.

While we have indicated that halogen-containing polymers in general are beneficiated by the stabilizers of this invention, we have found that these stabilizers are particularly useful when used in combination with the vinyl halide polymers such as the vinyl chlorides, the vinyl fiuorides, and the vinyl bromide polymers. We intend to include also copolymers of the aforementioned vinyl halides with vinyl 31601101501 with a vinyl ester of an aliphatic acid, such as vinyl acetate. A class of vinyl copolymers with which the stabilizers of this inventionimay be used to advantage are the vinyl chloride-vinyl acetate copolymers containing therein about 60% to 95% by weight of vinyl chloride. "This class of resins is disclosed in the patent to *Rei'ol, 1,935,577. Other useful vinyl resins are disclosed in the patent to Semen, 11,929,453. We may also use mixed resins, e. g. a mixture of polyvinyl chloride and a copolymer of polyvinyl chloride with polyvinyl acetate or polyacrylonitriie. Sat isfactory results are obtained with the vinylidene halides. Thus where we refer to a vinyl halide resin herein, we intend any of the foregoing vinyl halide-containing resins, it being understood that the vinylidene halides are equivalent thereto for the purposes of this invention. Generally these vinyl halide resins will contain a major amount of vinyl 'halidesuch as vinyl chloride and by the term major amount we mean in excess of vinyl halide up to and including 100% of a particular vinyl halide .or a 100% mixture of vinyl halides.

The base ester, for example, a mono-.ricinoleate of a polyhydric alcohol, suchasglycerine, maybe synthesized, or derived from the glyceride such as castor oil. It is clear that in any case, except where expensive fractionation procedures or special synthesis are employed, that the resultant product will be a mixture of mono-fatty acid esters and the higher esters. However, we intend by the term mono ester of apolyhydric alcohol to uncover a synthetic orderived ester wherein the quantities of reactants employed .in either the synthesis or the derivation are such as to favor the formation of the .mono .ester. Thus where castor oil, for example, is treated with glycerine to form the monoglyceride the amount of glycerin employed will bepreferably at least that which stoichiometrically ,favors monoglyceride formation, although it is recognized that the resultant productcontainsmonodiand tri-glyceride, as well as minor amounts of glycerides of acids other than ricinoileic .acid which are ordinarilypresen't in castor ,oil. The glycerolysis of any animal or vegetable .oil will result in a mixture of esters differing not only ,in degree of esteriiicationbut also .in ,thekind .of ester which will result. Such a mixture may then be acylated, or a separation of the monoglyceride effected by a suitable process, such as solvent extraction fractional crystallization from hot alcohol, and the monoglyceride then acylated. It has been found, however, ,to be unnecessary to isolatea particularmonoglyceride prior to acylation. The fatty acid radical in these partial esters of polyhydric alcohols is phroadlya .hydroxyealiphatic acyl group .containine from 18 final stripping is done at 140-150 .lizer was mille d .produced and used. Such examples are not to be construed as limiting the invention to the precise examples or conditions shown.

EXAMPLE I The synthesis of a typical stabilizer based on ricinoleic acid, glycerol, and acetic acid is described here. A mixture of 1868 grams of a refined grade of :castor oil and 553 grams of glycerol is heated to 160 (2., and 7.5 ml. of a calcium naphthenate solution (consisting of 5% ,ca-lciumasthe:naphthenate dissolved in mineral .spiirts) is added. The calcium naphthenate acts as a catalyst for the alcoholysis reaction between the oil and the glycerol The mixture is gradually heated to 210-2 15 C. and held for 3 hours with efficient stirring. After cooling to room .temperature and standing for hour the excess glycerol (lower layer) is removed by centrifuging. The product weighed 2200 grams. Its hydroxyl content was 13.8%, Gardner color, 3-5, andspecificgravity (25/25) about 1.00.

Since castor oil contains -85% of ricinoleic acid groups, minor components are the glycerides of other acids such as 'oleic, linoleic, and stearic.

The glyceride mixture, '2200 'g., is heated to 160-165 C. and acetylated by the careful portionwise addition of9l5 g. of'acetic anhydride. ,After the addition the mixture is heated at gentle reflux for one-half hour, transferred to a Claisen distilling flask and stripped .at 75-140 C. (pot temperature) and a reduced pressure of 130-40 mm. to remove most of the acetic acid. The C ./4-6 mm.

to remove The yield of stabilizer content was ,5.3-5.7%,

The hot residue is suction filtered traces of calciumsoaps. was 2470 g., its hydroxyl its saponification number was 300-310, acid 'number about 1.0, Gardner color,.6-,9, and specific gravity at '25/25 about 1:00.

In this particular illustration the amount of acetic anhydride was equivalent. to approximately 50% of the available "hydroxyl groups .in the glyceride -mixtur,e. Thus the product was a mixedalcohol-ester based on both ricinoleic and acetic acid groups with freealcoholic groups remaining to the extent of5-6%1by weight. Apart of these alcoholic ,groups are .on the ricinoleic acid radicals and ,theremain'der are attached to the glycerol radical.

EXAM-PLEjZ parts by weightofapolymerof vinyl chloride was mixed thoroughly with .50 parts'by weight of dioctyl phthalate and 3.0 parts by weight of various stabilizers. The stabilizers tested in separate batches were:

A. Strontium naphthenate B. 35% acetylated monoglyceride of .castoroil C. 50% acetylatecl monoglyceride of castor oil D. 65% acetylated monoglyceride of castor oil The mixture .of polymer, plasticizer, and stabi- .;for .itVZO minutes at 1.49" rC. .zon fiJlhQQg-lbll mill.

The ,zmillcd sheetawas .mcicjefiv pressure in a hydraulic press heated to 149? C.,

.togive a colorless, transparent, six inch square sheet approximately 0.090 inch thick. The sam- 6 catalysts such as litharge, lime, sodium hydroxide, etc. may be used. Catalysts, reaction weight, and reaction temperature should be such that the alcoholysis reaction proceeds substan- 100 parts by weight of a polymer containing 93% vinyl chloride and 7% vinyl acetate was 'mixed thoroughly with 50 parts by weight of dioctyl phthalate and 3.0 parts by weight of 50% acetylated monoglyceride of castor oil. The mixture of polymer, plasticizer, and stabilizer was milled for two minutes at 149 C. on a two roll mill. The milled sheet was molded for seconds under 2000 pounds per square inch pressure in a hydraulic press heated to 149 C. to give a colorless, transparent, six inch square sheet approximately 0.090 inch thick. Samples from the sheet containing acetylated mon'oglyceride-of castor oil showed much less discoloration after heating in an air circulating oven and exposure in an Eveready twin carbon are ultra violet light tester than similar samples from a sheet containing no stabilizer (see TableII).

Table I I 50% it y No ated stabmonoilizer glyceride of castor oil 1. Amount used (parts per 100 parts of polymer) 3,0, 2. Color of original sheet lNone. 3. Transparency of original sheet. Clear. 4. Blooming or exuding oi stabilizer Sheet: T

a. After 30 days standing at room temperal\one.. None.

ture. b. After 21 days inlight tester .do Do, ii.v Water absorption (percent gain in weight after. 7.0.". 6.9. immersion for 7-days at C. n 6. Heat loss (percent less in welght after 96 hrs. in 3.0. 3.2. an oven at 100 0.). 7. Heat stability (after 3 hrs. in oven at C.) Poor- Good. 8. Heat stability (after 30 min. inpven zit-174 C.) do Do. 9. Light stability (after 21 days in Eveready twin do.. Do. carbon are ultra violet light tester) The catalyst and temperatures given in Example I are not critical. Instead of caleiurn naphthenate, any of the well known alcoholysis fatty acid radical.

ples from the sheets containing partially acet- 5 tiaily to equilibrium. The temperature of, the ,ylated, monoglyceride of castor oil showed less acylation need only be such that the reaction discoloration after heating in an air-circulatbetween the alcohol groups and the acylation re- ..ing oven and exposure in an Eveready twin caractant takes place at a convenient rate. bon are ultra violet light tester than similar The ratio of reactants may be varied. In Exsheets containing no stabilizer 0r strontium naphl0 ample I above, the mol ratio of glycerol to castor thenate as a stabilizer (see Table I). oil is 3:1, respectively. Theoretically, the mono- Table 1 i59 acetylatet 307 acetylated 657 acetylated 50% acetylat-ed No Strontium U a u monoglyceride monoglycerldc monoglyceride monoglyceride stabmzer naphthenate of castor oil of castor oil of castor oil of g laAmount used (parts/100 parts or 0 3.0.. 3.0 3.0 3.0 3.0. polymer). '2. Color of original sheet None--. Very slight 3. 'lransparency'of original sheet Olear Clear 4. Blooming or exuding of stabilizer to None..-" None surface of sheet. 5. Water absorption (percent gain in 1.2

gang? after immersion for 7 days at 6. Heat loss (percent loss in weight after 2.6

96 hrs. in an oven at 100 0.). 7. Hegg sability (after 3 hrs. in oven at Poor 8. Hegi stibility (after 30 min. in oven at ...do.. 9. Light stability (after 21 days in Everdo eadytwincarbonarcultravioletlight 'tester).

EXAMPLE 3 glyccride requires a ratio of 2:1, but the reversible nature of the reaction is responsibe for an equilibrium mixture of mono-di-and triglyceridcs along with unreacted glycerol. To favor monoglyceride formation, a ratio greater than 2:1 may be used. Suitable products are obtained, however, at ratios above or below 2:1.

As indicated above an alternative route to this mixture of partial esters is by direct esterification of the polyhydric alcohol, e. g. glycerol with fatty acids, e. g. ricinoleic acid. The mixture of mono-di-and tri-glycerides and glycerol, for example, can be made equally well in this way although it is usually more convenient and economical to employ the alcoholysis reaction.

Throughout the foregoing description we have referred to ricinoleates as derived from castor oil and by direct synthesis from the component materials. However, instead of castor oil other animal or vegetable oils or mixtures thereof, such as cottonseed oil, fish oil, soy bean oil, linseed oil, etc. may be used. These are not as desirable as the preferred natural oil since it has been found that stabilizing activity is improved when free hydroxyl groups are initially present in the Oils-based on' ricinoleic, dihydroxystearic and the like, or synthetics thereof constitute the preferred class for use in accordance with this invention.

Stabilizing tests on the unacylated partial esters of glycerol derived from castor oil, cottonseed oil, etc. show that such substances are active, but a serious limitation on the use of such materials is their low compatibility with polymers and "'copoly'rners' containing substantial amounts'of polyvinyl halide, and the'tendency to migrate to the surface of films and sheets -so' intro'duced. Complete esteriflcation *gives "the highest degree of compatibility and produces materials which when used in larger amounts with .polyvinylhalides serve as excellent plasti- =-cizers. These latter materials are claimed in our loo-"pending application Ser. No.

less completely esterified material, "as contemplated by the present invention, maybe used. Partial esters of castor oil of varying degrees of acetylation have been carefully examined and the optimal range of acetylation for both compatibility and stabilizing activity is from 25% to below 75% of the available hydroxylgroups in the base partial ester.

Instead of partial acetylation to achieve efficient stabilization and complete and permanent miscibility, other aliphatic acid groups may be introduced as indicatedabove. The size-of the .acyligroup is not highly critical, but if the acid is of too high a molecular weight the shift from very polar .alcohol groups to increasingly less polar "ester groups will begin to reduce compatibility. Accordingly the preferred size of the acylating group'isin therange of from 1 to 6 carbon atoms.

It is desirable that the acyl group be dis- ,ributed over the alcohol groups in the various components of the partial ester mixture. The result is best obtained by partially acylating the mixture as illustrated in Example I above. An alternative method of mixing partial ester with completely acylatedpartial estercan yield a mixture which has the same over-all composition, but stabilizingtests show that the latter is less effective and less compatible. Thus the preferred. method of preparation is by acylation of the partial ester mixture to produce the desired product.

.In general, we blend the stabilizer-sci this invention in the resin, e. g. vinyl halide resins, in amounts ranging from .1 to 10 parts per 100 parts of polymer, either as the soleagent ..or;in combination with other well .known :plasticizing agents, such as the phthalates, phosphates, etc. Other resin additives such asflpigments, fillers, extenders, solvents, etc. may be present in the compositions of this invention in-the amounts ordinarily employed for the purposes indicated.

.-As indicated above, our co pending application .Ser. .No. .,139,128 covers acylated monohydrcxy fatty acid esters .of polyhydric alcohols .in which form 75% to 100% of the available hyroxyl groups have been acylated .by ;the same acylating agents as are disclosed herein. These materials acylated to this higher degree are disclosed therein as to being particularly useful .for plasticizing vinyl halide-containing resins. The .materials acylated to an extent less than 75% down to about of the available hydroxyl groups are contemp'late'd by *the present inven- .tion and are, :as indicated above, particularly :suited for use as stabilizers o'fivinyl halide-containing resins. I

Other modes oi 'applying "the principle of this invention may be employed "instead :of those specifically set forth above, changes being made as "regards the details herein-disclosed, provided the elements'set forth-many ofthe following claims, or the equivalent =o'f such be employed.

We, therefore, particularly point out and distinctly claim as our invention:

.fattyacid containing from 18 to 24- carbon'atoms and a polyhydricialcohol, in which ester from 25% to below of the availablefreehydroxyl groups. have been ."acylated with anvaliphatic acyl compound having the general formula:

wherein R is an aliphaticzacyl radicalof -from..1 to 6 carbon atoms and X is selected *fromthe :group consisting of '-"OH, SH, 'OR, -+'SR,.- and Ehalogen.

2. A composition inaccordance-awithclaimiil in which the polyvinyl halidecontaining polymeric zresin is polyvinyl chloride.

"3. A composition in accordance with claim 1 in which the aliphatic acid-"of high molecular weight is predominantlyricinoleic acid.

4. A composition invaccordance with-claimuzin which the mono-.esteriof av highzmoleeular weight fatty acid is derived .from'castor-oilby alcoholysis thereof with a polyhydric-alcohol.

5. A composition in accordance with claim "lain which the poly-hydric 'al'coholfis glycerol.

6. A composition comprising 'a vinyl chloridevinyl acetate .copolymersstabilized by the addition thereto of about .-3;parts ;'per 1 00 ,cparts of resin ;of .a partially :-acetylated;- partia1'ester-of ricinole'ic acid and-' glycerine,.:said ester being derived'i'rom castor oil by ialcoholysis :of said :castor foil with glycerine, said esterbeingsubsequently partially 'acetylated :to the "extent "of :from 25% to :below 75% of "the available *hydroxyl groups 'in r'sai'd partial ester.

7. A compositioninaaccordancewith claim 1'6 :in which the acetylation of the partial ester is completed to the extent of 50% of theavailable hydroxyl groups in said partial ester.

8. A composition in accordance with claim 1 in which the aliphatic acyl compound is an alkyl acylcompound.

"9. A composition in accordance with claim 1 in which R is 'acetyl.

OLIVER J. GRUMMITT. ROBERT "BLANK. EHERBERT 5F. "-SCHWARZ.

| References "Cited in the file oi "this patent UNITED STATES "PATENTS Number Name Date 2,156,956 Agens May '2, '1939 2,310,395 Carruthers Feb. '9, 1943 2,356,562 Berg et al .-"Aug.;22,';l944 2;500',91'8 Reuteret aln "Ma:r. 1-45-1950 2,584,998 Filachione .etal. ..Feb. 12,1952 

1. A COMPOSITION COMPRISING A POLYVINYL HALIDECONTAINING POLYMERIC RESIN AND AS A STABILIZER THEREFOR FROM ABOUT 0.1-10 PARTS PER 100 PARTS OF RESIN OF A MONO-ESTER OF A HIGH MOLECULAR WEIGHT FATTY ACID CONTAINING FROM 18 TO 24 CARBON ATOMS AND A POLYDRIC ALCOHOL, IN WHICH ESTER FROM 25% TO BELOW 75% OF THE AVAILABLE FREE HYDROXYL GROUPS HAVE BEEN ACYLATED WITH AN ALIPHATIC ACYL COMPOUND HAVING THE GENERAL FORMULA: 